Richard III: Power of Language and Own Villainy

Deformed in body and twisted in mind, Richard is in every way the dominant character of the play, to the extent that he is both the play’s protagonist and major villain. He is selfish, evil, corrupt, sadistic, and manipulative. His intelligence, political brilliance, and dazzling use of language keeps the audience fascinated and his subjects and rivals under his control. At the beginning of the play, it is made clear to the audience that Richard has no justification for seizing the throne. This is because England is obviously not oppressed or subject to tyranny as the lengthy civil war has just ended, and Richard’s oldest brother, King Edward IV, now sits on the throne. Richard himself, states that ‘All the clouds that loured upon our house’ (1. 1, 3), the house of York, has been dispelled by the ‘son of York’ (1. 1, 2), King Edward IV. However, Richard intends to upset the kingdom by seizing power for himself. He says that ‘since I cannot prove a lover to entertain these fair well-spoken days, I am determined to prove a villain’ (1. , 28). This simply means that since Richard was not made to be a lover, he has no use for peace, and will happily destroy peace with his crimes. This shows Richard’s unabashed enjoyment of his own villainy as he can so blithely toss aside all of the things that the rest of humanity cherishes. Richard III is an intense exploration of the psychology of evil, and that exploration is centred on the workings of Richard’s mind and the methods he uses to manipulate, control, and injure others for his own gain. Perhaps more than any other play by Shakespeare, the audience of Richard III experiences a complex, indefinite, and highly erratic relationship with the main character. Richard is clearly a villain as he declares outright in his very first speech that he intends to stop at nothing to achieve his ultimate goal of becoming king. However, despite his open allegiance to evil, he has such a charismatic and fascinating personality that, for much of the play, we are likely to sympathize with him, or are at least impressed by him. In this way, our relationship with Richard reflects the other characters’ relationships with him, conveying a powerful sense of the force of his personality. Even characters such as Lady Anne, who have an explicit knowledge of his wickedness, overlook his dishonesty and violent behaviour and allow themselves to be seduced by his brilliant wordplay, his skilful argumentation, and his relentless pursuit of his selfish desires. Richard’s long, fascinating soliloquys, in which he outlines his plans and gleefully confesses all his evil thoughts, are central to the audience’s experience of Richard. Shakespeare uses these soliloquys brilliantly to control the audience’s impression of Richard, enabling this manipulative protagonist to work his charm on the audience. In Act I, scene i, for example, Richard offers a pretext for his villainy towards others by pointing out that he is unloved, and that he is unloved because of his physical deformity. Richard himself is brutally honest about his appearance. He admits to being imperfectly shaped and blames premature birth for his condition. He knows that he is ‘not shaped for sportive tricks’ (1. 1, 14) and while others delight in ‘an amorous looking glass’ (1. , 14), his misshapen body creates a ‘shadow in the sun’ (1. 1, 26) that alienates him from others. Hence, Lady Anne calls Richard a ‘lump of foul deformity’ (1. 2, 57) in Act I, scene ii. This proves that Richard’s claim not only makes the other characters of the play seem like the villains for punishing him for his appearance, but also makes it easy for the audience to sympathize with Richard during the first scenes of the play and even hope that he will succeed despite his obvious villainy. It quickly becomes apparent, however, that Richard simply uses his deformity as a tool to gain the sympathy of others, including the audience. This is already noticeable in his very first speech as Richard seems to take a deliberate perverse delight in his outward shape. He chooses words such as, ‘cheated’, ‘deformed’, ‘unfinished’, ‘half made up’, ‘dogs bark’ at him as he passes by because of his ‘deformity’ to describe himself. Richard’s unabashed villainy is a much more natural part of his character than simple bitterness about his ugly body. Nevertheless, he still manages to use speech to win our trust, and he repeats this throughout his struggle to be crowned king. An interesting secondary theme of Richard III is the power of language, or the importance of language in achieving political power. Language may not always be a necessary instrument of power, but for Richard, it is a crucial weapon. As we have seen, it is with his extraordinary skills with words that allows him to ridicule, insult, taunt and deceive all who stand in his way to power. Richard’s skill with language and argument is what enables him to woo Lady Anne, have Clarence thrown in prison and blame the king for Clarence’s death, all at very little risk to himself. In conclusion, I feel Richard III’s unabashed enjoyment of both the power of language and his own villainy makes him a character worthy of both respect and admiration, and therefore I completely agree with this statement. This is because Richard’s unabashed power of language shows off the ingenious wit and intellectual cleverness of the character, actor and playwright, while his own villainy makes the play all the more fascinating and entertaining as his heinous acts become more chilling.

National Diabetes Fact

A Health Problem The diabetes is a disease which is characterized by the absence of insulin properly on the body. Also, the name diabetes has its origin in ancient Greece and Rome, and diabetes means â€Å"sweet†. In addition, this disease has been around the history of human beings for thousands of years. For example, there are manuscripts in Egyptian before of Christ that described to people to urinate frequently, and in Asia some doctors described people who suffered tiredness, skin boils and thirst.Recently, the diabetes has been grouped into three types which are type1 occurs when pancreas produces little or no insulin , type 2 is when the body becomes resistant to insulin or produces not enough blood sugar level, and gestational is in women who develop high blood sugar during pregnancy. Meanwhile, according to National Center for Chronic Disease Prevention and Health Promotion (NCCDPHP), in Its National Diabetes Fact Sheet 2011 (NDFS), based on data released by The Depar tment of Health and Human Services (DHHS) in year 2011, diabetes affects 25. million people 8. 3% of the U. S population and this disease has became in the seventh cause of death in the United States. Moreover, based on information from National Business Coalition on Health (NBCH) , in its Action Brief (AB) on February 2012, the diabetes expenses were of 174 billion annually in direct medical and indirect costs which had estimated for year 2007 in the United States.In simpler terms, the diabetes has became in serious health problem that produces diverse expenses to diabetics ,so an away to avoid expenses derived of this disease is research what factors can produce diabetes?. Finally, the diabetes produces high medical expenditures for hospital, physician, and prescription medicines to treat diabetes which is a disease caused for three serious disorders are related to obesity, genetic, and stress.First, the most common cause of diabetes is obesity which is related to physical inactiv ity, eating disorders, and genetic. Next, obesity is excess body fat which is commonly measured through mass index which is a ratio of body weight to height, so people are considered obese when their mass index is of 30 or higher ( based on information from National Institutes of Health (NIH), in its Clinical Guidelines on the Identification, Evaluation, and Treatment of Overweight and Obesity in Adults ( CGIETOOA) in year 1998) .Also, obesity is serious factor of risk for people because they are more susceptible to develop type 2 diabetes in which the body produces some but not enough insulin or is resistant to insulin; therefore, type 2 diabetes is associated to lack of physical activity. In other words, physical actives produce general health benefits such as blood sugar and pressure properly for adults and children because it is any form of exercise or movement such as household chores, yard work, walking, running, basketballs, or other sports.Moreover, insulin resistance has ob served metabolic abnormalities which are produced for morbidity, so obese subjects have this characteristic of insulin resistance because they lack of physical activities. In the second place, obesity is connect to diet improperly that has high levels of calories more than the body can metabolize, and this type of eating disorders has been result of fast food. In particular, people who eat more calories which are acquired through fast food or unhealthy food suffer of overweight.Too, overweight is characterized for abdominal fat that people can observe in increasing size of waist, hips, and deformation the body in specific areas. Due to, eating disorders produce overweight the metabolic body start to suffer changes that affected to insulin production because overeating produces a fighting into insulin production, so the body does not use insulin well and the result is unbalance in blood sugar level and people become in diabetics. Third, genetic frequently produce obesity that develop s diabetes.In this case, genetic is derived from parents or close relatives, so children are who suffers lineal consequences from obesity because it generally occurs in first year of life. Mainly, children are diagnostic diabetics because their bodies develop an insulin resistance or the pancreas does not produce insulin. As well, rare illnesses produce obesity as hypothyroidism which is disease produced abnormality of thyroid gland that does not produce quantities of hormone properly, among others.Finally, obesity is a cause of diabetes, but obesity generally develops type 2 diabetes which has a treatment through pills, diet and exercise, and this type of diabetes produce a codependency to pills. Typically, codependency to medicaments has raised abruptly, so this produce high expenditure in prescription medicines. Moreover, if population does not deplete the tendency of this disease, the expenses for effects of diabetes as hospital and physician too could continue incrementing. In effect, prescription medicines to treat diabetes increased 85. percent in the period of 1996 to 2003 (Olin, Gary 2006). To conclude, obesity that is risk factor for diabetes can avoid it through little changes in diet and style life more dynamic, so these little changes give positive effect economic and healthy. Second, the production of blood sugar levels is produced for genetic which is linked to factors as family history, racial and ethnic groups, metabolic reaction on diet , and rare gene. In addition, family history has an important connection with diabetes because this disease can be transmitted through of genes.In other words, diabetes has produced for a genetically disorder, so children born with diabetes because they have first degree relatives which are diabetics. Moreover, this characteristic is type1 diabetes in where the pancreas produces little or no insulin, so type 1 diabetics are insulin dependent and they daily need insulin shots to live. Furthermore, this type dia betes occurs in children, adolescents and adults, and type 1 diabetes is the most severe form of this disease in which people suffer serious complications of health as amputations, dialysis, diabetic comas, among others.Consequently, diabetics who suffer type 1 have more expenditure of hospital and treatment because their body develops complex situations of health. Next, racial and ethnic groups has a genetic predisposition diabetes, so natives and diverse tribes as American and Australian have people who suffer of diabetes. For example, some investigation have find that tribes in Arizona Pima and Papago their ethnic populations have the highest incidence of diabetes in the world, Seri a tribe in Mexico has suffered diabetes, and the Aborigines in Australia have developed diabetes (Nabhan, Gary Paul, 2004).In particular, ethnic groups , indigenous, native Americans, aborigines have involved diabetes (Nabhan, Gary Paul, 2004). Besides, the relation between racial and ethnic groups wh o has developed diabetes is caused for metabolic reaction on diet that has changed abruptly because their native food was plants which slow sugar and water loss qualities, so their metabolisms have adapted over time to the presence desert food.As a result, racial and ethic groups have changed native food by fast food, so the incidence of diabetes skyrocketed with heart disease and high cholesterol due to the metabolic reaction of these racial groups is different genetically. Another, factor is linked to appear of diabetes is particular gene called thrifty gene that indigenous hunter and gatherers have presumed to maintain as an adaptation to a feast –famine existence, so this thrifty gene has attributed the difference in blood insulin (Originally hypothesized by Neel, James in 1962).Subsequently, syndrome X (Nabhan, Gary Paul, 2004). has linked to genetic as responsible of appears diabetes, so racial and ethnic groups has increased risk of diabetes because they have access to groceries, alcohol and cigarettes and these groups expressed a cluster of conditions as high blood pressure, high triglycerides, cholesterol and obesity. Finally, ethnic groups have increased their predisposition of diabetes, and this produce more medical expenses to families who have relatives with diabetes.Finally, levels of blood sugar are lead to stress that is related to endocrine system, psychological aspects, and socioeconomic aspects. First, stress which is the state manifested by reaction that induced changes in biological system produces blood sugar improperly, and the endocrine system includes the master glands which are part of pancreas concerned with sugar metabolism. Second, an important part is the reaction of hypothalamus that is part of brain, so when a person is under physical or emotional stress its cerebral cortex sends messages at the hypothalamus.Then, hypothalamus produces releasing factors and these stimulate a part called the pituitary that secrete Adrenoco rticotropic hormones (ACTH) outer part of adrenal gland, in turn releases the glucocorticoid hormones that is blood and sugar raising, and TTH the thyroid gland secrete other substances. Consequently, ACTH and TTH thus cooperate in preparing the body to meet challenge of stress by making sugar available for cellular metabolism by increasing the metabolic rate of the cells.Moreover, a person that exposed a serious levels of stress repeats this process before mentioned sometimes, and this subject is exposed high blood sugar during this time so this person can develop diabetes, occasionally. Another aspect that is linked to stress is psychological that occurs when people are exposed to emotional circumstances, so diabetes appears when significant changes occurred in a person’s life .For example, adolescents who have attitudes and patterns of life adjustment, so they acquired the diabetes in middle age because a prominent though often suppressed of repressed conviction of having been starved of maternal love; in some cases caused for death of mother or a divorce. Inevitably, adolescents substitute calories for emotional nourishment, and teenagers with this emotional deprivation acquire a simulation of starvation that contributes a process of diabetes.Clearly, adolescents disturb their metabolism, so they involve in problem of obesity because adolescents suffer of night eating that only is one expression of emotional state; in these cases (Wolff, Harol G. in 1968) the therapy of obesity with problems of life adjustment is needed for releasing of depression. As well, socioeconomic aspects of stress have been incidents of diabetes, and people, who are involved in stressed situation because their low income and economic insecurity, are more predispose to illness.To illustrate, people that cope with urban poverty their life expectancy is less because they suffer chronic illness as heart, asthma, and diabetes. Furthermore, urban poverty is linked to inferior educ ation, racial discrimination, overcrowding, and crimes, among others; all these are factors stressors that affect the emotional balance of body, and these stressors become a chronic condition for residents. Consequently, stress is reaction of body when residents are exposed or involved to abnormal conditions which are ecological, psychological, social, biological, socioeconomics, genetic, among others.As a result, illnesses that are caused by stress as diabetes have incremented expenditure attributable to prescription medicines, hospitalization, medical appointments, and virtually diabetes caused for stress require a complex treatment physical and psychological for its management properly. On the whole, families could suffer financial problems by diabetes because this disease produces medical events. In short, diabetes is a chronic disease that affects insulin production of body, and the most common causes of this illness are obesity, predisposition genetic, and high or abnormal lev els of stress.Also, statistical data show high expenditures attributable to diabetes in United States mainly for hospitalization, medication, and physician support in managing this disease. In addition, obesity and the stress that are two of the three most common causes of diabetes will avoid through simple methods or routine that residents add to style life. For example, residents will avoid eating fast food and replace for health food, or they will try to practice sports. Moreover, citizens will look for method or technique that combats to stress properly.On the other hand, predisposition genetic that is one cause of diabetes will result complex situation, but this risk factor will be managing through of diagnostic pre-diabetes. In other words, financial costs will be regularized or controlled when communities and residents join and realize health programs about prevention and control of diabetes. Inevitably, this problematic situation requires of teamwork, and control of diabetes will reflect in billon dollars. Finally, population will be awareness that serious disease called diabetes has preventable.Work Cited Centers for Disease Control and Prevention. â€Å"National diabetes fact sheet: national estimates andgeneral information on diabetes and prediabetes in the United States, 2011†. Atlanta, GA: U. S. Department of Health and Human Services, Centers for Disease Control and Prevention, 2011. â€Å"Economic Costs Of Diabetes In The U. S. In 2007. † Diabetes Care 31. 3 (2008): 596-615. MEDLINE. Web. 1 Apr. 2012. Gordo, James S. Stress Management. Philadelphia: Chelsea House Publishers, 2001. pp. 13-52 Leahy Jack L. , Nathaniel G. Clark, and William T. Cefalu.Medical Management Of Diabetes Mellitus. M. Dekker, 2000. eBook Collection (EBSCOhost). Web. 1 Apr. 2012. Liberatore, Stephanie. †Q: what causes diabetes, and how does it affect a person’s health? † The Science teacher 76. 6 (2009):68. General OneFile. Web. 27 Mar. 201 2. Nabhan, Gary Paul. Why Some Like It Hot: food, genes, and cultural diversity. United Stated of America: Island Press, 2004. pp. 163-185 Olin, G. Proportion and Medical Expenditures of Adults Being Treated for Diabetes, 1996 and 2003.Statistical Brief #146. October 2006. Agency for Healthcare Research and Quality,Rockville, Md. http:/www. meps. ahrq. gov/mepsweb/data-files/publications/st146. pdf Paul, Tim Dall, and Plamen Nikolov. â€Å"Economic Costs Of Diabetes In The US In 2002. † Diabetes Care 26. 3 (2003): 917-932. MEDLINE. Web. 1 Apr. 2012. Peacock, Judith. â€Å"Chapter #1: What Is Diabetes?. † Diabetes (0-7368-0277-0). 4. Capstone Press, 2000. Health Source – Consumer Edition. Web. 1 Apr. 2012. Wollff, Harold G. Stress and Disease. Washington: Charles C Thomas, 1968. pp. 92-97

Compare and Contrast Ww1 & Ww2 Essay

The World Wars were in some ways similar but also, different. The World Wars had similarities in the way the wars were caused, how the wars ended, in regards to who lost, and propaganda. The casualties, the cost, and the military tactics however, were some of their differences. World War I was caused by the assassination of Archduke Francis Ferdinand of Austria in June 1914. However, World War II was caused by the political and economic instability in Germany, along with the bad conditions of the Treaty of Versailles . When the treaty of Versailles was put into affect, Germany acknowledged responsibility for the war, which also meant agreeing to pay enormous amounts of money for war reparations and losing land/territory to those who won the war . However, Germany agreed to this with a lot of bitterness. During World War II, Germany, as a nation, grew to really dislike the Treaty of Versailles because they thought it was unfair and that they were unable to pay the reparations due to the time period, the Great Depression. In addition, Hitler’s Rise to Power and his alliances in opposition to the Soviet Union. World War I was based on imperialism while World War II was a result of a clash of ideologies . WWI fought mainly to try and acquire territory. A s for WWII, it was a battle between Fascism and Communism . Even though there were some different causes to the wars, a similar cause would be the fact that the two wars were caused by a country or more than one country would want more power. During World War I, Germany was trying to get a hold of more power than it already had . The idea of having Germany gain more power alarmed many of the other countries, specifically France, England, and Russia, and forced them to go to war with Germany to be able to keep the balance of power within the nations. By World War II, Germany and Japan both believed that they did not have the amount of power they actually deserved . Germany wanted to regain the power it lost after World War I. As for Japan, it wanted to have a larger empire and to be taken in as a major power. Of course, the Allies were against this because they were fond with how everything was balanced at this time period. In the end, Germany would be the country that suffers and is defeated in both World War I and World War II. The difference in the defeat was that during WWI, the defeat was acknowledged, while in WWII, Hitler chose to fight until the final ending, which ultimately led to mass destruction . The outcome of World War I was that German, Russia, Austro-Hungarian and Ottoman Empires were militarily and politically defeated. The Austro-Hungarian and Ottoman Empires ceased to exist and the League of Nations emerged. The League of Nations was created in the hope of preventing another conflict . However, it failed due to the emergence of World War II. World War II ended with the Allied powers rising with victory, specifically giving USA and the Soviet Union the reputation of being the two most powerful nations, while Germany and Japan lost . After the League of Nations failed, the United Nations was established so that future conflicts could be handled by â€Å"international cooperation† and by preventing conflicts that could lead up to war . World War II had, by far, the most amount of deaths ever before. World War I had an estimated amount of 10 million dead, 21 million wounded, and 7.7 million missing or imprisoned, while World War II had more than 55 million civilian and military deaths . WWII was fought at a much greater scale and there were 7 times more casualties than in WWI. Also, World War I was located mostly in Europe, while World War II had included nearly the entire world. In addition to the casualties, the costs of the wars were outstanding. It is estimated that the cost of World War I cost about 380 billion dollars, while World War II cost about 42,000 billion dollars . Just the cost alone shows the great difference between World War I and World War II. Warfare methods had been the altered in regards of weaponry. During World War I, soldiers would fight from trenches and would use artillery, machine guns, early airplanes, and poisonous gas . There was little mobility during that time period. On the contrary, World War II fought using nuclear power and missiles . During this time period, many special operations were put into affect. An example of a special operation would be Operation Foxley, where the British military planned to assassinate Adolf Hitler (which was not really put into affect). In addition, submarines and tanks were also more heavily used and secret communication, or â€Å"code,† became more difficult to figure out, which benefitted them so that others would not understand their plan of attack, their location, etc. Radios were invented which were heavily used during WWII, while there were only landline phones in WWI . Something similar between World War I and World War II would be the propaganda that would be used to each countries benefit. During World War I and World War II, propaganda was something that both wars relied heavily upon. The propaganda was so heavily relied on due to the use of creating nationalism and supporting the war efforts on both sides and wars . An example would be how, even though the United States were reluctant in entering the war, when it finally joined, propaganda showed men fighting for their country and having to persuade other men to enlist. In addition, there would be that same type of propaganda for World War II. The propaganda helped to have the nation pull together as a whole and to, more importantly, support the war . Even though WWI and WWII seem close, they have had some major differences between them. In regards to political purposes, they were different. Economically, they were outstandingly different. Militarily, they had some similarities but some differences as well. Germany was a big factor that was important in both World War I and World War II. Overall, there were some similar qualities between both wars. In addition, there were some differences that can be seen between Worlds War II and I.

How the New Deal altered the role of the national government Essay

How the New Deal altered the role of the national government - Essay Example Majority of its legislation followed these purposes (Bryant). The New Deal changed the role of the national government, by expanding the power of the Federal Government and making it more responsible for the general welfare of the states. Since the U.S. became â€Å"united,† states enjoyed latitude in making laws and programs for their specific state needs and concerns. The Great Depression showed, however, that each state, or more so, a few ones, can generally impact the whole nation’s economic conditions. As a result, Roosevelt and his allies are convinced that they must change the national government from being a passive parent to a more aggressive parent handling the economy as a whole. After all, the Constitution states that the federal government has the power to regulate commerce between states and international trade and that it is authorized to generate laws that support the Constitution. Though the New Deal has been criticized as unconstitutional, it proved to greatly enhance the powers of the national government. During the New Deal of the Roosevelt administration, from 1933 to early 1935, the main goals were recovery and relief. The president and his advisers stressed the importance of the national government in creating laws that will stimulate the economy and provide new jobs. Roosevelt expressed to the American public about the alliances among â€Å"business and banking, agriculture and industry, and labor and capital,† in order to enlist them to the causes of the government (Bryant). On March 5, the president closed all the banks and called it a â€Å"bank holiday.† He influenced the Congress to pass a bill that helped the banks. That bill became law a few days later and the President asked the people to trust banks again and deposit their money once more into them. The banks reopened on Monday March 13th and Americans deposited their money again and the total effect was that they

Judicial Review Essay Example | Topics and Well Written Essays - 250 words

Judicial Review - Essay Example 78), because it is emphatically, the province and duty of the judicial government to say what the law is (Marbury Vs. Madison), and because the Constitution is the fundamental law, judges must give preference to it over ordinary laws† (11). It is the vested power of the judiciary branch of the government to strike down statutes which are inconsistent with the Constitution. In the event that a conflict shall arise between two laws, it is the duty and obligation of the Court to interpret the law and has the power to determine which among these laws are contrary to the intent of the supreme law of the land or the Constitution. According to Corwin, â€Å"Well-entrenched is the principle that the Constitution is superior to any ordinary act of the legislature, then, the Constitution, must govern the case to which they both apply† (8). The doctrine of judicial activism holds that the â€Å"federal judiciary should take an active role in using its powers to check the activitie s of the governmental bodies, when those bodies exceed their authorities â€Å"(Bardes, Shelley and Schmidt, 458). There are some judges who play as activists or a restraintists. An activist is one who presents the role of the judge as liberal wherein he applies the law in deciding the case and produces appropriate results.

Chapter 11, Who Owns History The Texas Textbook Controversy found in Essay

Chapter 11, Who Owns History The Texas Textbook Controversy found in Wheeler, Discovering the American Past, Volume II, 7th edition (pages 349-384) - Essay Example (Wheeler and Becker, Discovering the American Past, 354). It as necessitated an action to be taken by the Texas Board of Education in deciding what to give to the students and what to live out. It has brought such a heated debate amongst people from all fields. Many people are insisting that only few segments of history should be taught to the students. Therefore, it should include the role played by capitalist in the American economy and nation building, role played by military in their respective fields. In additions, roles played by Christians and their faith and the last should be the role played by republican figures. (Wheeler and Becker, Discovering the American Past, 361) If these changes are effected, it means that even the other states will be affected by the same. Texas as a state buys millions of books each and every year. They also make sure that their publications are of high standards, and this makes the other states willing their books. They also review their curriculu m once every ten years, in accordance with the Texas educational standards. The voting line, on what to be taught or not, will depend largely on the party lines; this is republicans and democrats. It is because individual parties believe there aspects that should be shown and others to be left out. There are those who think history in America has been diluted, while others believe that that history should just be re-written. It has, therefore, led to the creation of conservatives and liberals, who at the end of the day have different thoughts and opinions on American history (Wheeler and Becker, Discovering the American Past, 371). Conservatives are mostly outside Texas, and they are found in states such as California. Their argument is that, history should not be changed or re-written. It will in turn see their history books remain the same as before. Liberals, on the other hand,

Ethical Implications of Takeovers Case Study Example | Topics and Well Written Essays - 1000 words

Ethical Implications of Takeovers - Case Study Example The integrity question is the major ethical issue involved in this case, where Lisa is torn between challenging Mr. Jeffrey Anderson for overlooking the accounting discrepancies that have been noted on the financial statements of the Fragrance Company. The issue becomes an ethical dilemma for Lisa, because on the one hand, she needs to be true to her profession and also loyal to her organization, while she also needs to keep the acquired team close to her, since it is among the organizational workforce that Lisa will be working with. Whichever decision that Lisa chooses to take, she will cause detrimental suffering to other parties. This is because; if she chooses to overlook the accounting discrepancies in the Fragrance Company financial statements, the Home and Personal Care Products will suffer the detrimental effects of inaccurate basis of acquisition of the Fragrance Company. On the other hand, if she chooses to challenge Mr. Jeffrey Anderson over the discrepancies, she is likel y to distance herself from the newly acquired team that she will be working with, as part of the larger company.   Stakeholders involved in the ethical issue The stakeholders involved in this ethical issue are many. First, there is the shareholders of the Home and Personal Care Products, who will be directly affected by the acquisition of the Fragrance Company. This is because, the Home and Personal Care Products shareholders will be losing financially if the acquisition is completed based on the fraudulent and misrepresented financial statements.

International Marketing and communications Essay

International Marketing and communications - Essay Example The report is conclusive although the company should conduct future research in the market for it to be successful in the market. The company should follow the proposal in its operation to succeed in the new market. In the recent times companies have been undertaking measures to diversify their products and services in order to compete in the world market. The report gives an analysis of the entry mode, marketing strategies and other factors affecting the introduction of Verizon wireless mobile phones in the Iranian market. The report studies the effect of culture on a product, pricing and positioning. Research is done on the factors that affect the sale of the product in the country including the origin of the country which affects its marketing. The Iranian telecommunication sector has been experiencing massive growth in the past few years. Verizon wireless is a joint venture company in the telecommunications field which is based in the United States in New Jersey. The company is the second largest in this line in the United States and it reported an immense amount of revenue in the previous year as explained by Information Gatekeepers, Inc (2009).The company is well established and this can be seen through its expansion and mergers with other companies for example in 2009 it bought Alltel wireless according to Polishuk (2010). This is a clear indication that the company has enough resources to venture into the Iran telecommunications market and compete with local based companies by employing proper strategies. The company is one of the major carriers in the United States to use the CDMA technology. The company offers 3G data and voice services and it invests annually to expand and maintain its network as explained by Information Gate keepers Inc. (2009). The communication system in Iran has developed over the years an d the current plan is to modernize and expand the network with the aim of improving efficiency, increasing the urban

Critique of a Speech or Presentation (or editorial Essay - 1

Critique of a Speech or Presentation (or editorial - Essay Example This paper shall talk of how Obama manipulates his audience, or attempts to do so, through trying to confuse their view and hide the violence that his government and previous governments have done upon the nations which have been the targets of affirmative action. Previous instances of governmental actions shall be discussed in the paper as well. Obama begins his address by attempting an appeal to the emotions of the audience and also those who would get to know of it later. An appeal is thus made to the pathos of the listeners and the public of the United States of America. This appeal of pathos can be seen right towards the beginning of his speech, where he says, I would like to begin today by telling you about an American named Chris Stevens.... Chris Stevens loved his work. He took pride in the country he served, and saw dignity in the people he met. Two weeks ago, he travelled to Benghazi to review plans to establish a new cultural center and modernize a hospital. Thats when Americas compound came under attack. Along with three of his colleagues, Chris was killed in the city he helped to save (Obama). An appeal to the pathos and emotions of the audience in the United Nations and the people of America is understandable when one thinks of Obama’s position within the world of American politics. At a point of time that is close to the presidential elections, Obama attempts to make himself look like a person whom the common man of America can identify with is important. This is significant, especially if one takes into account the image that Barack Obama tries to project of himself- a man with a happy family life who has overcome racial problems to rise to the highest office in America and yet hasn’t lost touch with the lower sections of American society. All of these are appeals to the rhetoric of pathos that has always been a part of oratory. Continuing in the same strain in an attempt to appeal to

My country is russia Essay Example | Topics and Well Written Essays - 1250 words

My country is russia - Essay Example As Paltsev and Reilly (2009) point out, the US and Europe remain wary of energy rich nations like Saudi Arabia and Russia. Weak Institutions Russia ranks 133rd out of 144 countries in the World Economic Forum’s (WEF) Global Competitiveness Index (GCI) 2012-2013. According to Aidis and Estrin (2005), the formal institutional environment is the main barrier in developing entrepreneurship in Russia. Corruption is the important factor due to the low income of the governing classes. Business cannot develop when property rights are not fully enforced, and there is no rule of law which provides a conducive environment for entrepreneurship. Adequate finance for private enterprise to flourish, is also lacking. Social Unity 100 billionaires own 30% personal wealth in Russia compared to a global figure of less than 2%. Russia has a dearth in social capital, which is based on trust, values and networks. Putnam and Pollock opine that social capital is â€Å"the capacity for self-organizat ion and collective action in pursuit of some common good† (Menyashev & Polishchuk, p 2). Social capital can lead to economic development in two ways. One is by cutting transaction costs in the private sector and the other by finding a solution to the agency problem between the government and society. Policies Energy Scenario Russia has diversified to find new customers in China, Japan and North America for natural gas. The state-owned Gazprom owns most of the gas reserves and pipelines after the Soviet disintegration. It has also created new pipelines that would bypass the other ex-Soviet republics. It has the eighth largest oil reserves in the world. Production of oil increased from 2000 to 2004 after which there has been a slowdown. On the other hand, the electricity sector has been reorganized, which has attracted foreign players. Russia formed the Gas OPEC or Troika inspite of which, spare capacity has moved beyond the OPEC. When it moved beyond usual production by exploit ing the Arctic and East Siberia, US became oil independent. Moreover, many countries also increased their oil production. When it reduced subsidies, maximized energy efficiency, and upgraded energy infrastructure, it did not offer reform to the sector and the politicized firms could not take advantage of this development. The demand for oil reduced because of factors like energy efficiency measures, Europe bypassing Russia and the breakthrough in energy resources. This has been despite a growth in population of Russia. Weak Institutions Due to excessive bureaucracy, there is a growth in informal networks, which help to mobilize resources. There is intimacy and reciprocity in such networks. The entrepreneurs use only short-term finance which could point to an underdeveloped banking sector with poor collateral laws. The liability ratio is less than one which restricts the scale of enterprise whether as a startup or for the purpose of expansion. Trade credit in the form of loans from o ne firm to another in the supply chain is used and the profit earned is ploughed back into the business. Unclear bureaucratic policies increase the cost to business. According to Transparency International, public officials and civil servants, including the police, are the most corrupt institutions in Russia. In 2012, Russia ranked 101 in the overall quality of infrastructure. Though Russia is one of the most educated countries, the quality of education is declining. Life expectancy is low when compared to countries with similar GDP. The number of

Sound Leadership Essay Example for Free

Sound Leadership Essay The focus of leadership and the dynamics that make up sound leadership drives our day to day interaction in a continuous revolving world of business. Sound leadership is the core of every organization and solving its problems. Understanding leadership, its purpose, and dynamics enables executives to solve problems and maintain a competitive edge in a continuously changing business environment. In order to address the strategic implications that organizational behaviors have on leadership, justify the business needs of leadership, and codify the implications leadership has on organizational behaviors this paper will focus on the definition of different leadership styles and processes, how they relate to organizational behaviors within an organization, and how they form sound leadership. 14. November 2011 Throughout this course we have focused a significant amount of time discussing an organizational moment. The majority of the issues and solutions in every organizational moment evolved around leadership. Whether it was an absence of leadership or a directional change in leadership, leadership was at the core of every situation presented in the readings. Leadership is a behavior. The way an organization employs leadership,  controls a variety of influences that guides the company’s direction. The focus of leadership and the dynamics that make up sound leadership drives our day to day interaction in today’s world of business. Sound leadership is the core of every organization and solving its problems. Understanding leadership, its purpose, and dynamics enables executives to solve problems and maintain a competitive edge. In order to address the strategic implications that organizational behaviors have on leadership, justify the business needs of leadership, and codify the implications leadership has on organizational behaviors this paper will focus on the defining different leadership styles and processes, examine how they relate to organizational behaviors within an organization, and how they work to form sound leadership. According to Beebe Masterson (2006), leadership style is a relatively consistent pattern of behavior reflecting a leader’s beliefs and attitudes. It is the beliefs and attitudes that leadership forms toward the strategic goals of an organization that determines the direction of the company. In order for an organization to be successful they have to have buy-in. For an organization to have buy-in it establishes strategic goals that shape the direction of the organization. The leadership having buy-in, aligning their beliefs and attitudes toward the strategic goals of the organization, and relaying their beliefs and attitudes to their employees shapes the direction of the organization and provide a solid foundation for the organization to be successful. Leadership drives the mission of an organization and in order to impart these beliefs on their employee’s, leaders practice three basic leadership styles. Leadership styles determine the atmosphere of the organization. Understanding leadership and the many methods to employ it is as quintessential to an organization as its resources. According to Beebe and Masterson (2006), no two people practice the same methods of leadership; however, all people lead with three basic leadership styles; authoritarian, democratic, and laissez-faire. For this paper, it is not important to understand the definitions of each type of leadership style as it is to understand the fact that leadership styles determine the atmosphere and organizational behavior a company employs. Under authoritarian leadership  the leader dictates the work and tasks for each member. Members within an authoritarian leadership group are dependent on the leader to make decisions, are incapable of independent thought, and have difficulty navigating issues that arise within an organization. In democratic leadership leaders have more faith in the group and attempt to involve members in making decisions. Democratic leadership style encourages the development of employees, empowers members by involving them in the decision making process, and leaders provide the necessary support to allow the success of members. Laissez-faire leaders avoid dominating the group and assume the group will direct itself. Laissez-faire behavior is a complete avoidance of leading. â€Å"These non-leaders completely abdicate their leadership role and refuse to make decisions. This is a manager who is relatively inattentive, indifferent, frequently absent, and uninfluential† (Humphreys, 2001). These leadership styles greatly impact an organization and directly contribute to the directions and futures of a business. Leadership styles explain the persona leaders exude in managing their people. Leadership theorists incorporated processes into leadership to explain how leadership styles impact the performance of workers within an organization. Theorists have made their mark in the world of business. Over the past decades, researchers focused on defining the personal traits of effective leaders but ultimately concluded that it is not so much the traits as it is how individuals utilize these traits (Boseman, 2008). Theorists have focused their efforts toward understanding the processes of leadership to assist managers with leading their people and achieving the organization’s goals. Abraham Maslow, Clayton Alderfer, Victor Vroom, Edwin Locke, Henry Landsberger, Frederick Taylor, Paul Hersey, Ken Blanchard, Robert House, and Douglas McGregor studies in leadership have made major contributions to the world of business. Of these prolific theorists Maslow’s Hierarchy of Needs, Alderfer’s ERG Theory, House’s Path-Goal Theory, and Hersey and Blanchard’s Situational Leadership will be utilized to explain how leadership effect organizational behaviors. Abraham Maslow’s introduce his concept of leadership in 1943. Maslow’s  Hierarchy of Needs was based on motivational leadership. Maslow’s leadership concept is derived from the concept of a pyramid with five levels of employee needs; physiological needs, safety needs, love/belonging needs, esteem needs, and self-actualization needs. Clayton Alderfer, later in 1969, revised Maslow’s Hierarch of Needs into three categories; existence needs, relatedness needs, and growth needs. According to the studies of both theorists it is important for a leader to understand the needs of their people to effectively lead and motivate. Through their studies, these pioneers of leadership have established that the understanding that leaders have of their employee’s needs directly effects organizational behaviors and accomplishment of company goals and objectives. In 1971 Robert House’s introduce Path-Goal Theory. According to Lyons (2007), an effective leader is one who can help carve a path for subordinates that allow them to fulfill personal goals through the achievement of group and organizational goals. In path-goal theory a leader adopts either a directive, supportive, participative, or achievement oriented leadership style to accomplish this objective. The leadership style performed is dependent on two variables; characteristics of the employee and characteristics of the work environment. Based on both variables the leader practices directive, supportive, participative, or achievement oriented leadership. The leadership style practiced ensures the needs of the employee are fulfilled and organizational goals and objectives can be met. House’s path-goal theory is a needs base process that shapes the organizational behavior of an organization. Hersey and Blanchard’s situational leadership developed in 1974 distinguishes between four leadership styles that are characterized by a combination of task and relationship. Telling: High task, low relationship style Selling: High task, high relationship style Participating: Low task, high relationship style Delegating: Low task, low relationship style (Hitt, Miller, Colella, 2011) DeCaro, DeCaro Bowen-Thompson (2010) stated, â€Å"The model is useful in determining if a person’s leadership style is relationship or task oriented and if the situation such as task structure and leader members relationship, match the leader’s style to maximize performance.† Utilizing situational leadership a leader can accommodate an employee’s needs by varying their own behavior and applying the most suitable style for a given situation. By varying leadership style based on the employee’s needs a leader can manage organizational behaviors and achieve organizational goals and objectives. As one can see leadership and organizational behaviors work hand in hand. They both influence one another to meet the strategic goals and objectives of an organization. Hitt, Miller, Colella (2011), stated the strategic organizational behavior approach relies on the premise that people are the foundation of an organization’s competitive advantage. As evidence to this, leadership theorists developed processes based on the people within the organization. The processes developed guided organizational leaders in achieving the company’s goals and objectives. People and the leadership that shape the direction and culture of an organization play a vital role in establishing an organization’s organizational behaviors. Leadership is the quality to achieve desired results by giving the proper direction to the organization (Giri Santra, 2010). The influence that leadership and organizational behaviors have on a business establishes leadership as a critical and most vital asset an organization can employ. Throughout the eight weeks of this course we analyze an organizational behavior moment that discussed leadership struggles within organizations. The leadership struggles faced in the organizational moments relay the importance of leadership within an organization. In the case study, â€Å"Bright and Dedicated What more can you ask for?† Anita Lockwood is a perfect example of an authoritative leader. Anita rules with an iron fist over Susan  and her employees. Anita never empowers Susan to run the finance department and as a result Susan’s leadership development is hindered. The importance of Anita’s and Susan’s moment in organizational behavior is it displays the effects that authoritarian leadership style has and how it impacts others. In an authoritative leadership environment the organizational goals and objectives are met, however at the expense of the professional development of people within the organization. In situational leadership it is sometimes necessary to practice authoritative leadership in order to stimulate the growth during the training process of learning a new job or position. Once the training process is over it is important that the leader is able to transition out of the authoritative leadership style and into one that continues to allow their personnel to grow and develop within the organization. â€Å"The Two Presidents† is another organization moment that provides an example of the importance of leadership to business. In this case study Alvin Thomas displays the attributes of a democratic leader. Alvin exhibits an active role of leadership, empowers his employees to make decisions, and establishes goals and objectives based on organizational dynamics. Thomas’s leadership allows the university, the people around him, and himself to prosper due to his style of leadership. A democratic leadership style broods balance and creates a positive environment that allows a leader to be directive, supportive, participative, or achievement oriented when necessary. The importance of this characteristic is the leader understanding their employees. Understanding employees enables leaders to meet the needs of their employees and companies to maintain their competitive edge. The last organizational moment that I would like to discuss in support of the argument of why leadership is important to business is â€Å"A Sea Change in Staffing at Leapfrog Innovations, Inc.† In this case study Dick Eaton dons the role of a laissez-faire leader. Dick’s hands-off approach failed him miserably in the end. Due to his negligence his company experienced a high turn-over rate of personnel and had no foundation for stability once the three long-time employees begun to transition to other opportunities. This left Dick holding the bag per say and his company in shambles with no  direction and a bleak future. Dick’s experience was an extreme case of laissez-faire leadership. There are instances where this style of leadership is appropriate. Laissez-faire leadership is appropriate when personnel are performing and meeting the expectations of the leader and goals of the organization. In Dick’s case he was a laissez-faire leader from beginning to end. He took a huge gamble in placing all his faith in the leadership of one individual to run his company and when they decided to leave the experience, knowledge base, and foundation of his company left also. Three different case studies, three different leadership styles, and three different outcomes; the key theme to note in each case is the importance of leadership. Leadership is one of the key fundamental building blocks of running a business and is as quintessential to an organization as its resources. According to Giri Santra (2010), Leadership is the quality to achieve desired results by giving proper direction to the organization. In order to achieve the desired results leaders utilize motivation to motivate employees toward achieving the organization’s common goal. The assumption that leadership is a set of behaviors that can actually be observed, measured, and developed is critical to the development of any process (Kanji, 2008). Leadership theorist understood the importance of leadership to business and developed processes to assist leaders in understanding what motivates people. Each topic discussed in this paper depicts the basics of leadership. The purpose for this paper was to understand how leadership affects business and relates to organization behaviors. The organizational behaviors a company employs and the practice of leadership has a significant impact on the strategic implications of an organization. Business challenges effects every industry and creates vast opportunities to establish sound organization behaviors to support sound leadership. It is paramount that the organizational behaviors that a company employs support its leadership. In summary there are four key points to note in the importance of leadership to a business: a. Leadership styles vary in types and it is important that businesses adopt practices that best fits their organization and people. b. Leadership Theorist improvements in processes that define leadership, helps organizations to understand, manage, and lead personnel. c. Leadership and Organizational behaviors work together to form sound leadership. d. Sound leadership within an organization creates a healthy work environment. The importance of leadership to an organization could mean its success or could lead to its demise. The choice of leadership style is crucial to the success of business operations and hence also the ultimate performance of the company (Juhl, Kristensen, Kanji, Batley, 2000). Every business, organization, or group of people striving together to accomplish a common goal needs only one thing to be successful, Leadership! At the forefront of every fortune 500 company, military, government, and country is sound leadership to meet company objectives and goals. No matter which style of leadership is practiced, it is leadership at the foundation of every organization that drives the company. The strategic implications that organizational behaviors have on leadership, codify the importance of leadership to business. The implications that leadership, leadership styles, and leadership processes have on an organization directly relate to the organizational behaviors within an organization and how they assemble to establish sound leadership. References Beebe, S. A., Masterson, J. T. (2006). Communicating in Small Groups: Principles and Practices, Eighth Edition. Bostin, Massachusetts: Allyn and Bacon. Boseman, G. (2008). Effective Leadership in a Changing World. Journal of Financial Service Professionals, 62(3), 36-38. Retrieved from EBSCOhost. DeCaro, F. P., DeCaro, N., Bowen-Thompson, F. O. (2010). An Examination of Leadership Styles of Minority Business Entrepreneurs: A Case Study of Public Contracts. Journal of Business Economic Studies, 16(2), 72-78. Retrieved from EBSCOhost. Giri, V. N., Santra, T. (2010). Effects of Job Experience, Career Stage, and Hierarchy on Leadership Style. Singapore Management Review, 32(1), 85-93. Retrieved from EBSCOhost. Hitt, M. A., Miller, C. C., Colella, A. (2011). Leadership. Organizational Behavior (Third Ed), CH 8, Hoboken, NJ: John Wiley Sons, Inc. Humphreys, J. H. (2001). Transformational and Transactional Leader Behavior. Journal of Management Research (09725814), 1(3), 149. Retrieved from EBSCOhost. Juhl, H. J., Kristensen, K. K., Kanji, G. K., Batley, T. W. (2000). Quality Management: A Comparison of Cultural Differences. Total Quality Management, 11(1), 57-65. doi:10.1080/0954412007026 Kanji, G. K. (2008). Leadership is prime: How do you measure Leadership Excellence? Total Quality Management Business Excellence, 19(4), 417-427. doi:10.1080/14783360802002834 Lyons, P. (2007). A Leadership Development Model to Improve Organizational Competitiveness. Advances in Competitiveness Research, 15(1/2), 103-115. Retrieved from EBSCOhost.

Violence of mass Media Essay Example for Free

Violence of mass Media Essay The research involves the study of possible relationships between violence and mass media. In the study, a sample frame was obtained in order to be tested utilizing four different tests, which validates and determines possible relationships between violence and media, media preferences and age violent behavior occurrence, empathy and gender variations, and time commitment against violence. The research results obtained show increasingly violent behavior among males than females. The commitment time of males manifesting violent behavior is higher as compared to females. Moreover, the preferences of these respondents that manifest such behavioral pattern are noted to generally prefer violent media forms, most prominently, television and movie showing violent acts. Violence of Mass Media: Introductory (MINI ESSAY) Most of the public concern and scientific study of the perceived violent reality of media centers around the effects of viewing televised violence. The effect that many think of first is modeling, when people imitate violent behavior that they see on television. The research on the different effects has been driven by diverse theoretical frameworks for example, studies of behavioral effects have most often been driven by social learning/cognitive theory, and studies of attitudinal effects often draw on behavioral imitation (Wells and Ernest, 1997 p. 227). The following section examines several different effects of media violence in turn and the evidence supporting each of them. Technological advances have dramatically increased the availability of violent entertainment. The introduction of television was critical, particularly in making violent entertainment more available to children. More recently, cable systems, videocassette recorders, and video games have increased exposure (Singer and Singer, 2001 p. 372). (Preiss, 2007 p. 153). The research approaches the study of media violence in this study by looking at the various effects of the violent view of the world presented in media. This study of the perceived reality of media violence focuses on the psychological processes involved and the weight of the evidence supporting the existence of those effects (Wells and Ernest, 1997 p. 229). Later in the study, the research looks at individual differences among those who are attracted to or repelled by media violence and longitudinal studies probing for long-term effects. Next, the study will look at one of the newest areas of concern, violent video games. Finally, the study addresses the question of what may be done to provide balance to this violent perceived reality and thus mitigate the negative effects of media violence. Violence of Mass Media Introduction Although humans have used violence in cautionary tales to teach the lessons of morality in almost every culture and historical era, the teaching has usually been closely tied to the tale. Active discussion of the moral points seems to be necessary for the lesson to â€Å"take. † Thus, many adults and children who watch cautionary violence television programs by themselves may fail to make the desired moral connection. Instead, they learn the lesson of ‘Instrumentality,† the lesson that violence can be used as an effective instrument to get something of value or to compel others to do one’s bidding (Wells and Ernest, 1997 p. 231). Perhaps literature has always been bloody, hut even the fastest and most dedicated reader cannot make it through a printed description of more than a few murders a day by reading Shakespeare, Mickey Spillane, and Norman Mailer. A look at 4 hours of prime-time television, or a couple of rental videotape movies can easily provide several times as many deaths, maiming, rapes, and beatings as could be encountered in the same amount of time spent reading periodicals and books. The amount of violence is not the only factor of importance in the impact of television and movie experience. These moving image media, with their close depictions of what individuals can see and hear, are much more engaging of our sensory attention than is the reading of abstract symbols on paper, which must be translated and reconstructed into an approximation of sensory experience. What the study must now examine is whether the large volume and sensory increase of 20th-Century media violence, especially movies and television, has actually caused people to do more violence than they otherwise may have done. Methodology Sample Frame The sample frame utilized in the study involves 150 respondents from elementary schools as well as daycare centers within the locale of midstream city. Based on the inclusion criteria, the elementary schools recruited possess a private orientation, with religious inclination to Catholicism as the basic moral ground, while the daycare center should be networked with private school. As with the gender division of the sample size, 82 boys and 68 girls from grades 4 and 5, with an average age of 9. 99 (s. d. =0. 74). In terms of the racial criteria of the samples involved, European American comprises 58% while African American is 24%, providing the picture of the community. Data Gathering Procedure In the data gathering procedures, the study utilized a form of four different questionnaires with order counterbalanced. The following details inquired through the questionnaires are the demographic information, which includes gender, age, grade and mother’s education, preferences on forms of media utilization, survey forms of real-life violence through Attitudes Towards Violence Scale: Child Version (ATVC), appraisal of the respondents’ characters towards violence through KID-screen for adolescent violence exposure (KID-SAVE); and lastly, the extent of the sample’s empathy through Children’s empathy questionnaire (CEQ). After which, the researchers obtain the favorite form categorization for television as to sports, fighting, destruction, real people, or no favorites. On the form of internet, the respondents are categorized according to their preferences, such as chat room, instant messages, video games, no favorite internet activities and no access to internet. Review of Related Literature Moat American families bought their first television set during the early to mid-1950s. As more and more homes had television sets and more and more people began to watch on a regular basis, scholars began to study this new phenomenon, and the first studies about television content were published (Head, 1954; Smythe, 1954; cited in Well and Ernest, 1997 p. 262). Moreover, the first congressional hearings about television, focusing particularly on television violence, were convened in 1954. Research on television content and its effects was particularly stimulated by the forces that affected the United States during the late 1960s, notably national turmoil, civil rights and the women’s movement. Two national commissions were appointed to uncover the dynamics of these Forces on society. In essence, the agendas of these commissions set the stage for early and ongoing research on media images. The national turmoil that rocked the country after the assassinations of Martin Luther King Jr. and Bobby Kennedy stimulated concern about violence in society and in the media. The National Commission on the Causes and Prevention of Violence (NCCPV) was appointed to examine violence in society, including violence on television, and commissioned one study to ascertain the amount of violence on television (Gerbner, 1969; cited in Preiss, 2007 p. 162). Continued national unrest, as well as concerns about television’s impact on Americans, further encouraged researchers to pursue this line of study. Financial assistance was also provided by increased government funding for research about television violence inn 1969, even before the report of the NCCPV released. Congress appropriated 1$ million and set up the Surgeon General’s Scientific Advisory Committee on Television and Social Behavior and this committee funded 23 projects, dealing primarily with violence on television and its effects (Gerbner, 1972; Surgeon Generals Scientific Advising Committee, 1972; cited in Wells and Ernest, 1997 p. 232). Although interest in television violence faded somewhat during the 1960s, congressional concern about media violence again increased during the 1990, culminating in the development of ratings for television programs and the V-chip technology. Concern with civil rights, during the late 1960s and early 1970s, contributed to the proliferation of studies on minority images. The Kerner Commission, appointed by President Johnson to investigate racial disturbances in many US. cities, charged this these disturbances could be traced, in part, to the U. S (Preiss, 2007 p. 158). There have been few investigations into the effects of print media violence. The most extensive investigation, 1w the Canadian Royal Commission on Violence in the Communications Industry† in 1977, reported details of the amount of violence in print media but made no contributions to our understanding of what violence-causing effects may stem from reading violent material (Royal Commission, 1977; cited in Preiss, 2007 p. 156). Most likely for reason’ previously discussed—less intensity and less of it—violence in books, newspapers and magazines has been of less concern to citizens. An exception was violence in comic books, which became a political issue in the United States in 1954. At the time, comic books were read avidly by many young boys. Today, they read comic books less and spend more time with television. Despite their name, comic books were largely not funny at all; they were violent and tended to emphasize the violent heroism of characters with whom the children could identify. However, many comic books glorified criminals and their brutality. Congressional hearings were held which, in turn, resulted in the comic hook industry adopting self-censorship of violence in a successful effort to head off passage of laws, which would have imposed government restrictions. The evidence that comic books actually did bring young readers to using violence and committing crimes was drawn from the collective experience of law enforcement officers and psychiatric workers (Berkowitz, 1973; cited in (Wells and Ernest, 1997 p. 233). In one such instance, teen-age boys in Boston doused with gasoline and set on fire a down-and-out, liquor-dazed man they found. There was no apparent motive other than to try out what they had seen on a television program (Singer and Singer, 2001 p. 370). Another example is the batch of imitative suicides that have occurred following television and theater showings of the movie The Deer Hunter, in which a scene occurs showing a man with a pistol playing—and losing—a game of Russian Roulette (Wells and Ernest, 1997 p. 232). According to Huesmann and Taylor (2006), media violence poses an eventual threat to the public social equilibrium significantly through the influence of violence and aggression. According to their study, fictional television and film violence contribute to both a short-term and a long-term increase in aggression and violence in young viewers. According to the research conducted by Browne and Hamilton-Giachritsis (2005), there has been frequent evidence that suggest the linkage of child violent behavioral acts, and the incidence and frequency of violent media exposure. Such media forms induce arousal, thought influence, and emotional deviations, which consequently increases the likelihood of aggression and fearful behavioral patterns, most especially in males (Preiss, 2007 p. 162). The presence of prosocial effects is undeniable. Very few people who enjoy television and movies containing violence feel that they are endangered by it, and appear most willing to take any risks. However, it would be incorrect to conclude that violence needs to be present in entertainment in order to be of interest to people. The television and film industry has merely used violent action as a reliable and inexpensive means of attracting a certain level of viewer interest in otherwise very repetitive stories (Singer and Singer, 2001 p. 368). Thus, â€Å"action† and production values† (which is to say, violent action), is regularly added to scripts to make them more attractive. Nevertheless, research on college students indicates that violence, itself, is not what they are interested in so much as in the quality of action and story associated with the violence (Preiss, 2007 p. 161). Unfortunately, media executives find it difficult to accommodate such interests. The high quality of writing needed to create stories, which can stand on their own without the addition of violence is very costly. There are only a limited number of writers, whose skill is great enough to provide consistently attractive nonviolent stories. Station and network program decision makers generally take what they consider to be the safe path of â€Å"plenty of action and production values† in order to assure that their programs will attract the teen-age and young adult audience members greatly desired by advertisers of consumer products (Wells and Ernest, 1997 p. 233). Berkowitz and his co-researchers have also established that the violence present in abundance in films such as Straw Dogs and Walking Tail especially influences viewers to act violently, for the film violence is presented as the solution to outrages perpetrated by others. Revenge and justification are extremely potent factors in determining whether violence will occur. If an aroused person who has freedom of action then encounters violence on a television screen, the violence may act as a potent cue to draw forth her own violence, to the degree that what is shown on screen resembles and pulls into memory previous occasions on which she used violence (U. S. Senate Committee on Commerce, 1972; cited in Singer and Singer, 2001 p. 368). Tannenbaum and Zillmann (1975; cited in Singer and Singer, 2001 p. 367) demonstrated how arousal may be reshaped, in a very dramatic way. After arousing college males by showing them very sexy pictures, they found that whether the men subsequently tried to accomplish sexual or violent behavior depended on the cues that were presented to them. In other words, a person may be aroused by something sexual, watch a murder on television, and become violent instead of erotic (Singer and Singer, 2001 p. 367). Thus, there is a potential link between sex and subsequent violence that may be activated by television and film violence cues. Findings After calculating the means and standard deviations of the results from KID-SAVE, ATVC and CEQ obtained form the samples, a series of t-tests was applied to scrutinize the gender variations on the Frequency and Impact Total scales of the KID-SAVE, the ATVC Total, and the CEQ Total. Such analysis revealed gender differences on the KID-SAVE Frequency Total scale, t(148) = 2. 71, p0. 01. Boys were reported to be in a higher stakes of violent behaviors, although no significant gender variations were found on the KID-SAVE Impact Total scale. On the other hand, the analysis on boys and girls’ ATVC and CEQ Total scales, t (148) = 2. 62, p0. 05, and t(148) = -3. 72, p0. 01, revealed significant differences; gender differences from these two tests indicate that boys have higher tendencies for violent behaviors, while girls have higher behavioral tendencies for empathy. Indices of multicollinearity were examined and no problems were identified. After which, regression analyses were initiated to determine the probabilities of real-life violence from the data of Total Frequency and Total Impact scales of the KIDSAVE, exposure to the four indicators of media violence (video game, television, movies, and Internet) and the total CEQ score. From the results of obtained, it revealed that individual variations increase the probabilities of negative impact from violent video games. Considering the latter conclusion, 17 girls playing violent games are reported to demonstrate frequent negative behavior. From the said respondents, the manifestation of negative behavior maybe more prominent due to norm violation present (Funk Buchman, 1996a). Considering other media forms presented to the respondents, the results show that movie violence is the most prominent influence. On the other hand, the manifestations of negative behavior have been linked to the increased time commitment and content of movie being watched (Anderson, Huston, Schmitt, Linebarger, Wright, 2001). Time reported may have influenced the failure to find a relationship between television violence exposure and the study variables. Considering the presented categories and gender differences, boys have been reported to devote 5. 6 hours of viewing per week, while girls reported 2. 8 hours weekly. Conclusion In the conclusion of the study, violent behaviors and utilization of mass media showing violent scenes possess a link that induces violent behavioral patterns among viewers. In terms of gender variations, males have been noted to demonstrate violent acts as compared to females. Moreover, males have noted to demonstrate increase time commitment to preferred violent movies, which are also the most preferred media forms, than with females. On the other hand, females are noted to be more emphatic as compared to males. Generally, the research has provided significant relationship between violence and mass media. References Anderson, D. R. , Huston, A. C. , Schmitt, K. L. , Linebarger, D. L. , Wright, J. C. (2001). Early childhood television viewing and adolescentbehavior. Monographs of the Society for Research in Child Development, 66 (1, Serial No. 264). Browne , P. D. , Hamilton-Giachritsis , C. (2005, February 19). The influence of violent media on children and adolescents: a public-health approach. The Lancet, 365, 702-710. Funk, J. B. (2004, January). Violence exposure in real-life, video games, television, movies, and the internet: is there desensitization?. Journal of Adolescence, 27, 23–39.

Multifunctional Porous Organics Synthesis

Multifunctional Porous Organics Synthesis TITLE OF WORK The synthesis and characterisation of functionalized porous organics Abstract Lophine based radicals have been studied for many years due to their photochromic nature, recent literature has seen attempts to connect two radicals to carbon based backbones. In this report we will discuss attaching six lophine molecules to a single backbone which is a phosphazene ring. Cyclophosphazene rings have a unique conformation allowing for supramolecular architectures to be formed by varying the substituents, these architectures range from 0-2D structures. The hexalophine molecule exhibits 1D channels due its unique conformation which leads to the formation of a porous material. Porous organics are of high interest in recent literature due to them being a cheaper, less toxic alternative to MOFs as well as having the ability to be modified and tailored easily due to the simple starting materials. In this report we shall state synthetic pathways from simple molecular building blocks to hexalophine (32%) and two derivatives, compound 4 (46%) and 5 (15%). These two derivatives have the potential to increase pore stability. This report will also include the oxidation of hexalophine to its radical species which were found to display photochromic properties and it is also believed that this material could contain light gated pores which are closed in the dimer form of the product but then open upon irradiation of UV of 365nm. 1. INTRODUCTION 1.0 Properties and potential uses of Lophine This report will feature chemistry based upon the triphenylimidazolyl based radicals (TPIRs) as well as the dimer form hexaarylbiimidazole (HABI). Lophine (2,4,5-triphenyl-1H-imidazole) is a heterocyclic imidazole derivative where three phenyl rings are attached to the imidazole ring (figure 1), these imidazole derivatives are an area of importance due to the many interesting properties it possesses. Lophine has been of interest to researchers for many years with its chemiluminescent properties being first discovered in 1877 by Radziszewski.1 The oxidation of the lophine molecule follows the reaction scheme below, where lophine is oxidised to the TPIR radical state via addion of base and treatment with Fe forming one of six dimers both in solution and the solid state (figure 2). These materials display photochromic, thermochromic and piezochromic properties. The mechanism of photochromism of the lophine dimer is the homolytic cleavage of the 2C-1N bond of the dimer by irradiation wit h light, forming two lophine radicals.2 The fast colour change associated with this dimer opening means there is a potential use in display screens or as the basis for molecular switches, where irradiation with light opens the dimer forming the radical in turn switching the external component On/Off. These possible applications have caused a focus on creating methods to manipulate and control the colour of these materials and as well as to increase the rate of switching.3 The colour of the radical form is dependent upon the substituents on the ring, the more conjugated the system the further toward the red side of the spectrum the colour.4 Lophine displays piezochromic properties in its solid state, upon applying pressure lophine crystals the colour change of yellow to blue/green has been observed, this occurs via the radical dissociation of the 1N-1N dimer bond.5 Other more unusual modes have been of dimerization such as the 2C-2C have now also been isolated, this mode features a u nusually long C-C bond.3 Figure 1 The structure of Lophine (2,4,5-triphenyl-1H-imidazole) Another interesting lophyl radical derivative is the 1,8-TPID-naphthalene radical which consists of 2 lophine radicals connected by a naphthalene ring. 1,8-TPID-naphthalene has been characterised in the solid state by Abe et al; who studied the photoreactivity of the compound. 1,8-TPID-naphthalene allowed the group to fix two radicals onto a backbone meaning that the radicals were in close proximity and could dimerise easily as opposed to two radicals not connected via a backbone which first need to find eachother in order for dimerization to occur (figure 3). They found that the dimer could be cleaved photochemically giving the diradical and then could be thermally converted back to the dimer.6 They also found that the formation of a peroxide bridge was much more common than previous literature had accounted for. This bridging occurred when the 1,8-TPID-naphthalene radical was placed under an O2 atmosphere.7 This peroxide bridge formation is very important as when oxygen quenches th e spin to form the closed shell peroxide it does so irreversibly meaning the material is no longer photochromic. It was then shown that this peroxide degradation pathway can be generalised for the chromic dimers of TPIR materials, with non-tethered TPIRs forming similar peroxide bridges.8 A recent development by the same research group has also shown how a thiophene substituted phenoxyl-imidazole radical complex (PIC) can generate two non-equivalent radical upon irradiation with UV light. The colour change can be fine-tuned from tens of seconds to nanoseconds, however a sensitivity to lower wavelengths of light meant that applications were limited. This problem was rectified by adding a phenyl group to the 5 position of the thiophene ring.9 Figure 2 The six potential dimerization modes of two lophyl radicals.3 Figure 3 Illustrates the reversible conversion of 1,8-TPID-naphthalene between its radical and dimer forms. 1.1 Hexa-substituted Phophazene Rings, Tectons and Crystal Engineering A key component of this project was the exploitation of the Phosphazene ring as soft tecton; a tecton is a molecular building block that interacts with sticky sites, formally known as supramolecular synthons, via spatial arrangements to induce the formation of supramolecular aggregates. The search for new tectons is a hot area of research due to the constantly growing field of crystal engineering where the aim is to produce functional single crystal materials using intermolecular interactions. The arrangement of molecules in solid state structures is largely dependent on striking a fine balance between intramolecular forces and packing interactions, knowledge of these forces is key to the field of crystal engineering.10 In general, hard tectons interact via more robust synthons than soft tectons and therefore usually crystallise with unambiguous geometries. Whereas soft tectons and less robust synthons allow for the formation of supramolecular isomers (figure 4).11 These tectons allo w for many functional materials to be formed in a one pot synthesis, they also have the ability to be carefully adjusted to alter and improve upon their functionality.12 Cyclophosphazenes are extremely soft tectons that interact with soft synthons to give a large variety of supramolecular architectures in the solid state. The conformation of the cyclophosphazenes is also very interesting as three substituents reside above the plane of the ring and three below (figure 5). It was found that small modifications to the substituents attached to the ring gave supramolecular architectures ranging from 0D to 2D structures (figure 6) such as include monomer, dimer, cyclic hexamer, zigzag chain, linear chain, double chain, graphite-type sheet, rectangular grid and hexagonal close-packed sheet. Such variety of structures came from the easy rotation about the exocyclic P-N bonds, which allowed variable directionalities for all of the N-H bonds. 11   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   3a)  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   3b) Figure 4a) Shows benzene-1,4-dicarboxylic acid a classic example of a hard tecton. 4b) shows a silanetriol a classic soft tecton. Figure 5 Conformation of a Hexa-substituted Phosphazene Ring. Figure 6 Schematic representations of aggregation patterns of (RNH)6P3N3 in the solid state.11 1.2 Magnetism and Magnetic Frustration The materials we aim to make during this project once appropriately oxidised should go on to form dimers which when irradiated with UV light form discrete radicals containing unpaired electrons thus giving each radical an associated magnetic moment. Neutral organic radicals tend to be paramagnetic and exhibit Curie- Weiss behaviour, where the spin vectors of the unpaired electrons are randomly aligned above the Curie temperature (Tc), which is the critical temperature below which the long ordered state is established, unless a magnetic field is applied. If spin vectors are parallel to each other below the Curie temperature then the material is ferromagnetic, if the spin vectors are aligned antiparallel to one another the material is antiferromagnetic.13 Due to the geometry of the phosphazene ring (three substituents pointing up above the plane of the ring and three below) there is the possibility of forming a 2D triangular lattice of spins if the substituents are organic radicals.   This could possibly lead to geometric magnetic frustration due to the fact that the two nearest neighbours to a spin are themselves nearest neighbours and therefore antiferromagnetic couplings cannot be satisfied (figure 7).14 This can lead to very interesting magnetic properties. Most solid state examples of this geometric frustration tend to be transition metal oxides, however, studies have been done on organic systems that also distribute geometric frustration.13 One example of this is m-MPYNNP+ which is a spin  ½ organic radical that upon dimerization forms a 2D triangular lattice which demonstrates the aforementioned geometric frustration.14 The issue of spin frustration has been around for a long time as Quantum spin liquids (QSL) were first theoretically proposed by Anderson many years ago which are now a hot topic of research due to the realisation of these QSLs in organic materials such as k-(ET)2-CH2(CN)3, which has a near perfect triangular lattice with angles very close to 120 °.15 A QSL is an exotic ground state where interacting spins continuously fluctuate with no formation of   low range magnetic order even at sufficiently low temperatures.16 Figure 7 Antiferromagnetic coupling cannot be fulfilled causing geometric magnetic frustration. 1.3 Porous Materials Porous materials are as important as ever due to their wide spread use in several fields such as catalysis and gas absorption,17 meaning they can play a critical role in the route to solving our growing energy shortage problems. Porous materials are instantly associated with materials such as zeolites, metal organic framework (MOF) and organic polymers. MOFs are characterised by their tuneable pores and inherent flexibility which more classical carbon or oxide based structures do not possess, this gives a wide range of applications for MOFs such as gas storage, separation, drug delivery or catalysis.18 Porous organics have been discovered in nature but are largely created synthetically and approaches often need to be coupled with knowledge of crystal engineering. These materials are often held together by directional forces which form extended frameworks of noncovalent interactions such as Ï€- Ï€ interactions, hydrogen bonding or coordinate bonding (figure 8).17 Like zeolites a nd MOFs porous organics have the ability to selectively absorb atoms and molecules in the gas phase.19 There are many positives to these porous organics, they are often cheaper to synthesise and less toxic as well as being far less dense than metal containing MOFs. Figure 8 One example of a Porous Organic by Sozzani et al. 1.4 P3N3 Hexalophine The chemistry of P3N3 Hexalophine incorporates much of the chemistry discussed above and has many interesting properties. The P3N3 Hexalophine molecule consists of six lophine substituents attached to the phosphazene ring via a P-O bond (figure 9). Previous work in the Robertson group found that the solid state structure of Hexalophine consisted of a pseudo hexagonal motif giving rise to 1D channels that run parallel to the stacking axis (figure 10). The molecule maintained its D3 symmetry in the solid state. The phenyl rings twist to maximise pi-stacking interaction and the 3 imidazole nitrogen atoms form hydrogen bonds to a central water molecule. There are 4 pi-pi interactions that stabilise this structure, the molecules are in a slipped conformation allowing the phenyl and imidazole to rings overlap. Other non-covalent interactions such as van der Waals interactions also help to stabilise the structure. The high symmetry of the structure which comes from the hexa substituted phos phazene ring (three above the plane of the ring and three below) gives an equal distribution of intermolecular forces giving a high probability of forming a stable porous structure. IGA measurements with CO2 loading at 195K shows a Type I isotherm with absorption reaching 8cm3g-1 at a pressure of 700mmHg confirming the materials microporosity. However only a small fraction of the void space contained CO2. Figure 9 The structure of Hexalophine. Figure 10 The crystal structure of Hexalophine, illustrating the 1D channels. 1.5 Aim of Project The aim of this project is to combine our knowledge of the chemistry of both lophine radical systems and cyclophosphazene rings to find elegant synthetic routes which will improve upon the porous properties of hexalophine. This will be done by varying the ring substituents to increase stability of the pores and to improve its gas absorption properties. Three lophine derivatives have been identified as plausible candidates for thid are where two of the phenyl groups on the lophine will be replaced by two thiophene rings and two pyridine rings respectively, with the position of the nitrogen in the pyridine ring being varied depending upon the synthetic pathway (figure 11). We wish to synthesise and fully characterise these derivatives including growing single crystals for structural studies via X-ray crystallography. Also a stoichiometric controlled oxidation of the hexalophine material to its neutral radical/dimer pair is required in order to further investigate the properties of hexa lophine such as the possibility of creating a photochromic material that has light gated pores that open on irradiation with UV light. R=  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   or  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   or Figure 11 the synthetic targets of this project. 2. Results and discussion 2.0 Hexa-benzaldehyde Synthesis The first step in this synthetic project involved attaching six benzaldehyde units to the phosphazene ring via a P-O oxygen bond. This was achieved by reacting the phosphonitrillic chloride trimer along with 6 equivalents of 4-hydroxybenzaldehyde, potassium carbonate in dry THF (figure 12). The reaction was monitored with 31P NMR which showed completion when only a singlet was present in the spectra indicating full substitution. This produced the compound 1 which was the precursor for many of the subsequent reactions. The reaction gave the desired product in a fairly low yield (45%). Whilst the yield was slightly low the FT-IR showed all of the characteristic absorptions such as C=O (1697cm-1) and CAr-CAr (1585cm-1). 31P NMR was conducted and showed a sharp singlet at 7.08ppm which indicated full substitution on the phosphazene ring as all of the environments are equivalent. 1H NMR was also conducted and show a singlet at 9.87ppm with an integration of 6Hs which was as expected for t he 6 aldehyde protons, two doublets were found in the aromatic region and integrated to 12Hs each which was correct for the number of protons expected. The CHN analysis was almost perfect with less than 0.2% difference from the calculated values, this indicated that the product was of high purity. Mass spectometry also indicated that the desired product had been synthesized as a [M+Na]+ peak was detected at 884. Figure 12 The reaction scheme for the synthesis of 1. 2.1 Synthesis of Hexalophine and Hexalophine derivatives 2.1.0 Using Diketones The synthesis of hexalophine and hexalophine derivatives is important due to their porous properties which can be of great importance in fields such as gas storage and catalysis. The method for attaching six lophine units to the ring was a ring condensation of 1 on the six benzaldehyde units attached to the phosphazene ring using a synthesis based upon Radziszewskis synthesis.1 The product 2 was achieved by reacting 1 along with six equivalents of benzil, ammonium acetate in excess in glacial acetic acid (figure 13). The yield for 2 was quite poor (32%), the FT-IR showed all of the characteristic peaks such as CAr-H (3055cm-1), C=N (1604cm-1) and CAr=CAr (1538cm-1) indicating the desired product had been formed. This was further confirmed by both the 31P and 1H NMR, the 31P NMR showed a singlet at 8.36ppm which indicates full substitution on the phosphazene ring. The 1H NMR showed a singlet at 12.65ppm which had an integration equal to 6Hs which is representative of the 6 imidazole N -Hs, it also showed multiplets in the aromatic region with an integration of 84Hs which is exactly the number of aromatic hydrogens in the desired product. CHN analysis of the product correlated well with the desired structure, especially when three molecules of water were factored into the calculation. It is unsurprising that this compound also contained water due to its porous nature.   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   NH4OAc   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   Acetic acid (6eq.) Figure 13 The reaction scheme for the synthesis of 2. Another reaction designed based upon the ring condensation reaction was the synthesis of 4. This synthesis builds upon the diketone functionality as above, however, in this reaction the R groups of the diketone thenil were thiophene rings as opposed to the phenyl rings of benzil. Thenil like benzil was reacted with 1 and ammonium acetate in glacial acetic acid (figure 14). The yield for this compound, whilst better than 2, was still fairly low (46%). FT-IR showed the characteristic peaks such as CAr-H (3071cm-1), CAr=CAr (1643cm-1) and C=N (1607cm-1) indicating the target molecule had been synthesised. The 31P NMR showed a singlet at 8.26ppm again indicating full substitution. The 1H NMR showed a singlet 12.91ppm with an integration of 6Hs representative of the 6 imidazole N-H hydrogens, it also showed multiplets in the aromatic region with an integration of 60 which was again exactly what was required for the number of aromatic hydrogens, indicating the correct product had been synt hesised. The CHN analysis was close to the theorectical values required especially when four water molecules were factored in, again this is unsurprising as this material like 2 is also expected to be porous.   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   NH4OAc   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   Acetic acid (6eq.) Figure 14 The reaction scheme for the synthesis of 4. Like thenil and benzil, pyridil is also a diketone where the two R groups are heterocycles, in this case the two heterocycles are pyridine rings. Pyridil was used again with the classical Radziszewski based synthesis to synthesise the compound 5 (Figure 15). The yield for this compound was very low (15%) due to a lot of mass lost upon recrystallization and decomposition upon heating. The FT-IR showed the correct absorptions for the key functional groups such as C=N (1600cm-1) and P=N (1158cm-1) indicating that the target compound had been synthesised. However large OH absorption band (3349cm-1) was also present showing that the product contained a considerable amount of water or ethanol. CHN analysis of the compound showed a vast difference in carbon and nitrogen values when compared to the theoretical values indicating some impurities in the sample. The fact that the product contained considerable amounts solvent would also skew the result of the CHN analysis somewhat.   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   NH4OAc   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   Acetic acid (6eq.) Figure 15 The reaction scheme for the synthesis of 5. 2.1.1 Using Aldehydes for an alternative preparation The idea of using aldehydes such as pyridine carboxyaldehyde and benzaldehyde as opposed to the diketones used above was born when questioning on how we could stabilise the pores in the materials we wished to synthesise as larger groups could be added to these aldehyde starting materials. An alternative synthesis of 2 using twelve equivalents of benzaldehyde is illustrated in figure 16. The reaction was left to reflux for 7 days however the 31P NMR showed a multiplet indicating that full substitution had not occurred or a mix of products was present. Unfortunately, this was a reoccurring theme as the failed synthesis of 3 using twelve equivalents of pyridine carboxyaldehyde (figure 17) also showed a multiplet in the 31P NMR. Benzaldehyde (12 eq.) Figure 16 The reaction scheme for and alternative preparation of 2. Carboxyaldehyde (12 eq.) Figure 17 The reaction scheme for compound 3. 2.2 Oxidation of Hexalophine and its derivatives The oxidation of hexalophine is of great interest due to the potential properties it may possess, such as it possessing photochromic properties which may lead to light gated pores. For this oxidation an excess of potassium hydroxide was used to create the anion before 50 equivalents of the classical oxidising agent potassium ferrocyanide (III) were used to perform a one electron oxidation to the radical species 6, a yellow to orange colour change is associated with the formation of the radical species. This radical species quickly dimerises and an orange to yellow colour change is associated with this. Upon irradiation with UV light (365nm) the dimer opens to form two radicals, the colour change associated with this was yellow to purple displaying the photochromic behaviour of this compound (figure 18). The radical species is stable for a number of hours in the solid state unless gentle heating is applied which induces dimerization again and the colour change of purple to yellow is a ssociated with this. FT-IR showed characteristic absorbances of CAr-H (2955cm-1), C-N (1301cm-1) and P=N (1198cm-1) which are present in the desired product. The thiophene hexalophine derivative 4 was also oxidised using the same classical oxidation conditions as above to form its radical species 7. Upon separation the system formed 3 layers, an organic layer, an aqueous layer and a solid substance formed which was soluble in neither. Both the organic layer and solid substance were irradiated with UV light to test for photochromic properties however neither displayed a colour change and thus further testing of this material via UV/Vis spectroscopy is required to determine its nature. Figure 18 A RBF containing the hexalophine dimer and radical, the purple is the radical species, the yellow is the dimer species. 3. Conclusions and further work The aim of this project was to synthesise and characterise functionalised porous organics based upon hexalophine as well as to perform oxidations to the radical species and study their properties such as photochromism. For the most part the aim of the project has been met as two derivatives of hexalophine (4 and 5) and hexalophine (2) itself have been synthesised from simple molecular building blocks and characterised using a range of spectroscopic techniques such as NMR, FT-IR and CHN analysis. The next step in the characterisation of these materials would be to gain crystal structures via x-ray crystallography to show the packing arrangement of these molecules and to prove the existence of pores with in the molecule created from the unique conformation of the phosphazene ring. Additionally, once crystal structures have been gained gas absorption test should be taken to test both the gas uptake properties and selectivity of certain gases. Yields for these experiments were quite low and the aldehyde reactions did not demonstrate full substitution onto the ring, one possible solution would be to try the reaction in a Parr pressure reactor. The oxidation of hexalophine was carried out with great success as the experiment demonstrated the proposed photochromic nature of the material, also the stability of this material with respect to air was very surprising. If possible crystal structures for this material should be obtained in order to investigate further the possibility of light gated pores which when the molecule is in the dimer form are closed but once in the radical form are open. 4. Experimental details 4.0 Ma